Abstract
In situ hydrothermal reduction of Np(VI) to Np(IV) in the presence of methylenediphosphonic acid (C1P2) results
in the crystallization of Np[CH2(PO3)2](H2O)2 (NpC1P2-1). Similar reactions have been explored with U(VI) resulting
in the isolation of the U(IV) diphosphonate U[CH2(PO3)2](H2O) (UC1P2-1), and the two U(VI) diphosphonates
(UO2)2[CH2(PO3)2](H2O)3 · H2O (UC1P2-2) and UO2[CH2(PO3H)2](H2O) (UC1P2-3). Single crystal diffraction studies
of NpC1P2-1 reveal that it consists of eight-coordinate Np(IV) bound by diphosphonate anions and two coordinating
water molecules to create a polar three-dimensional framework structure wherein the water molecules reside in
channels. The structure of UC1P2-1 is similar to that of NpC1P2-1 in that it also adopts a three-dimensional
structure. However, the U(IV) centers are seven-coordinate with only a single bound water molecule. UC1P2-2
and UC1P2-3 both contain U(VI). Nevertheless, their structures are quite distinct with UC1P2-2 being composed
of corrugated layers containing UO6 and UO7 units bridged by C1P2; whereas, UC1P2-3 is found as a polar
three-dimensional network structure containing only pentagonal bipyramidal U(VI). Fluorescence measurements on
UC1P2-2 and UC1P2-3 exhibit emission from the uranyl moieties with classical vibronic fine-structure.